Theoretical Study of the Relative Stabilities of the alpha /beta 3-[XW11O39]m- Lacunary Polyoxometalates (X = P, Si).

Danielle Laurencin (1) , Anna Proust (1) , Hélène Gérard (2)

1 CIM2 - Laboratoire de Chimie Inorganique et Matériaux Moléculaires
2 LCT - Laboratoire de chimie théorique

A computational DFT-B3PW91 study of the relative stability of the monolacunary Keggin polyoxotungstates alpha and beta 3-[XW11O39]m- (X = P, m = 7; X = Si, m = 8) was performed. The influence of the nature of different grafted cations and of the central anion XO4n- on the relative stabilities of the lacunary isomers was analyzed. From these results, an interpretation of the structural difference in the metallic frameworks of alpha -[PW11O39{Ru(DMSO)3(H2O)}]5-, alpha -[PW11O39{Ru(C6H6)(H2O)}]5-, and beta 3-[SiW11O39{Ru(DMSO)3(H2O)}]6- is proposed, and conclusions are drawn as to how to favor the formation of beta 3 derivs. in future syntheses.

Mots clés: polyoxométallates; DFT; Keggin lacunaire

Domaines: Chimie inorganique

Danielle Laurencin, Anna Proust, Hélène Gérard. Theoretical Study of the Relative Stabilities of the alpha /beta 3-[XW11O39]m- Lacunary Polyoxometalates (X = P, Si).. Inorganic Chemistry, 2008, 47, pp.7888-7893. ⟨10.1021/ic800539j⟩. ⟨hal-00358162⟩